Abstract : Industrially relevant atropisomeric diphosphines such as 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP), 6,6'-bis(diphenylphosphino)-2,2',3,3'-tetrahydro-5,5'-bi-1,4-benzodioxin (SYNPHOS), and 5,5'-bis(diphenylphosphino)-2,2,2',2'-tetrafluoro-4,4'-bi-1,3-benzodioxole (DIFLUORPHOS) have demonstrated their efficiency in the copper-catalyzed asym. conjugate addn. of various dialkylzincs to α-aryl enones, α-aryl dienones, and cyclic dienones. Excellent 1,4- or 1,6-regioselectivities and enantioselectivities (up to 97% ee) were attained, even with challenging sterically hindered Michael acceptors.